JP2018531780A - 酸素還元反応触媒 - Google Patents
酸素還元反応触媒 Download PDFInfo
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- JP2018531780A JP2018531780A JP2018512240A JP2018512240A JP2018531780A JP 2018531780 A JP2018531780 A JP 2018531780A JP 2018512240 A JP2018512240 A JP 2018512240A JP 2018512240 A JP2018512240 A JP 2018512240A JP 2018531780 A JP2018531780 A JP 2018531780A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000001301 oxygen Substances 0.000 title claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 24
- 238000006722 reduction reaction Methods 0.000 title claims abstract description 17
- 239000007809 chemical reaction catalyst Substances 0.000 title description 2
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 175
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003054 catalyst Substances 0.000 claims abstract description 96
- 239000000463 material Substances 0.000 claims abstract description 89
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 66
- 239000011148 porous material Substances 0.000 claims abstract description 51
- 229910052742 iron Inorganic materials 0.000 claims abstract description 49
- 238000000197 pyrolysis Methods 0.000 claims abstract description 44
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 35
- 239000010941 cobalt Substances 0.000 claims abstract description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000012018 catalyst precursor Substances 0.000 claims description 39
- 239000000446 fuel Substances 0.000 claims description 32
- 239000003446 ligand Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 14
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 230000000694 effects Effects 0.000 description 42
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 20
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003801 milling Methods 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001308 synthesis method Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000005580 one pot reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- 239000013132 MOF-5 Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- LJJZKMDEQVYRJX-UHFFFAOYSA-N 4,5,6-tripyridin-2-yltriazine Chemical compound N1=CC=CC=C1C1=NN=NC(C=2N=CC=CC=2)=C1C1=CC=CC=N1 LJJZKMDEQVYRJX-UHFFFAOYSA-N 0.000 description 1
- 229920003934 Aciplex® Polymers 0.000 description 1
- 229920003937 Aquivion® Polymers 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- -1 Co (II) Chemical class 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 239000012692 Fe precursor Substances 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KLTWGRFNJPLFDA-UHFFFAOYSA-N benzimidazolide Chemical compound C1=CC=C2[N-]C=NC2=C1 KLTWGRFNJPLFDA-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004422 calculation algorithm Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- MWJGORHQXRXGAH-UHFFFAOYSA-N cobalt(2+) imidazol-3-ide Chemical compound N1(C=CN=C1)[Co]N1C=CN=C1 MWJGORHQXRXGAH-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 239000013141 crystalline metal-organic framework Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000034964 establishment of cell polarity Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001722 flash pyrolysis Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical class Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000013105 nano metal-organic framework Substances 0.000 description 1
- 239000013289 nano-metal-organic framework Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract
【選択図】図2
Description
0.7cm3g−1以上の内部細孔比容積を有する金属有機骨格(MOF)材料を提供することと、
鉄源及び/又はコバルト源を提供することと、
MOF材料を鉄源及び/又はコバルト源と一緒に熱分解して触媒を形成することと
を含み、
MOF材料が窒素を含み、且つ/又はMOF材料が窒素源並びに鉄源及び/又はコバルト源と一緒に熱分解される方法を提供する。
最大空洞サイズが12Å以上の等方性空洞形状を有する金属有機骨格(MOF)材料を提供することと、
鉄源及び/又はコバルト源を提供することと、
MOF材料を鉄源及び/又はコバルト源と一緒に熱分解して触媒を形成することと
を含み、
MOF材料が窒素を含み、且つ/又はMOF材料が窒素源並びに鉄源及び/又はコバルト源と一緒に熱分解される方法を提供する。
金属有機骨格(MOF)配位子及びMOF金属源を提供することと、
鉄源及び/又はコバルト源を提供することと、
任意選択的に、窒素源を提供することと、
0.7cm3g−1以上の内部細孔比容積を有するMOF材料を含む触媒前駆体を得るのに十分なエネルギー源を提供することと、
触媒前駆体を熱分解してORR触媒を得ることと
を含む方法を提供する。
金属有機骨格(MOF)配位子及びMOF金属源を提供することと、
鉄源及び/又はコバルト源を提供することと、
任意選択的に、窒素源を提供することと、
最大空洞サイズが12Å以上の等方性空洞形状を有するMOF材料を含む触媒前駆体を得るのに十分なエネルギー源を提供することと、
触媒前駆体を熱分解してORR触媒を得ることと
を含む方法を提供する。
内部細孔比容積
各MOFの結晶学的構造を用い、内部細孔比容積を計算した。この目的のために、各固体について文献に記されている単結晶データに従い、結晶構造をまず構築した。レナードジョーンズパラメータ及び電荷を用い、幾何学を最適化して、構造内の原子の位置を決定した。この場合では、レナードジョーンズパラメータのユニバーサルフォースフィールド(UFF:Universal Force Field)を考慮した。最適化された構造の全容積内で、且つDuren等(T. Duren、F. Millange、G. Ferey、K.S. Walton、R.Q. Snurr、J. Phys. Chem. C、2007、111、15350)によってこれまでに報告されている方略に従い、次いで、0Åの理論上のプローブサイズを用いて結晶学的単位格子の全容積を決定した。単位格子は、結晶性固体の巨視的構造を予測することのできる、三次元におけるその繰り返しによって決定される結晶性固体の最小容積である。単位格子の容積は、単位格子全体で0Åの理論上のプローブを移動させることによって決定された。これにより、原子が占有する空間内か又は自由容積すなわち細孔内かのどちらにプローブが局在していたかが、モンテカルロアルゴリズムを使用して決定された。このような方略は、単位格子の自由細孔容積を単位格子内に存在する原子の質量で除すことによる巨視的な多孔質固体の内部細孔比容積の決定を可能にした。
構造原子に同じパラメータ(UFF)を用い、Gelb及びGubbinsの方法論(L.D. Gelb、K.E. Gubbins、Pore size distributions in porous glasses: a computer simulation study、Langmuir、1999、15、305-308)を使用して、細孔サイズ分布(PSD:pore size distribution)を計算した。これは、構造体内に収めることのできる最大の球体をモンテカルロ計算を使用して決定するために、漸増する直径の球体を単位格子の自由容積内に位置付ける試みからなる。明らかに、球体は単位格子の自由細孔容積を占有し、構造体の原子が占有する空間と重ね合うことはできない。この方法論を用いると、細孔サイズ分布(PSD)、すなわち構造体内に所与のサイズの細孔が見出される確率を決定することが可能である。次にこのPSD曲線を用いると、等方性空洞サイズ、並びに化学種が構造体の1つの空洞から別の空洞に移ることを可能にする枠のサイズを推定することが可能である。
所与のMOF粉末、Fe(II)酢酸塩、及び1,10−フェナントロリンから、乾式ボールミル粉砕手法によって触媒前駆体を調製した。
第1のシリーズの実施例では、全ての触媒を同様の様式で調製及び試験し、唯一の相違点は触媒前駆体を調製するために用いたMOFの性質及び構造であった。
プリスチンな等方性MOFにおける空洞サイズと熱分解生成物のORR活性との相関性をより良く実証するため、酢酸鉄、1,10−フェナントロリン、及びMOFのミル粉砕後のプリスチンなMOFのXRDパターン(ひいてはそれらの空洞サイズ)を維持するためにミル粉砕速度を100rpmに低減させた。これらの条件において、全てのMOFで100rpmのミル粉砕後に変化のないXRDパターンが観察された(ここでは示さない)。したがってこの第2のシリーズの実施例では、熱分解前の触媒前駆体は、プリスチンなMOFの空洞サイズによって特徴付けられる。合成条件は、その他の点では第1のシリーズの実施例で示したものと同一であった。各MOFについて、最適温度(図4に示す)を熱分解温度として選択した。
方法1によって調製された触媒前駆体は、MOF中に存在する第1の遷移金属を揮発性生成物と一緒に除去し、且つMOFの炭化を引き起こすのに十分な温度におけるN2、Ar等の不活性ガス中でまず熱分解し(ランプ加熱方式又はフラッシュ加熱方式)、次に、触媒の多孔性を更に増加させ、且つ触媒の表面上に存在する金属−NxCy部位の数を増加させるエッチングガス(NH3、CO2、CO等)中で熱分解することができる。
いわゆるワンポット手法によって触媒前駆体を調製した。典型的に、秤量した量のFe(II)Ac、1,10−フェナントロリン、MOF配位子、及びZnOの乾燥粉末を磨砕又はボールミル粉砕によって混合した。次に、MOFの形成がソルボサーマル条件又は機械的条件下で起こった。この触媒前駆体を次に、例示的合成方法1で各MOFについて既に特定されている最適温度において流動するアンモニア中で熱分解した。
Cat−28(本発明の実施例)
DMF(6ml)及びジルコニアミル粉砕ボールを含むジルコニウムミルポットに、ZnO(3.0047g、37mmol)、eIm(7.1495g、72mmol)、(NH4)2SO4(0.7541g、7mmol)、Fe(Ac)2(0.1188g、0.68mmol)、及び1,10−フェナントロリン(2.377g、13mmol)を入れた。この混合物をFritschのミルで400rpmにおいて30分間磨砕した。得られた薄いピンク色の固体を空気中で乾燥させた。次にこの生成物を、例示的合成方法1に開示される方法に従って950℃の流動するアンモニア中で熱分解した。
ZnO(2.2803g、28mmol)、mIm(5.0349g、61mmol)、Fe(Ac)2(0.0679g)、及び1,10−フェナントロリン(1.2092g、6.7mmol)を磨砕して均質な混合物にし、次にAr下でソルボサーマルボンベ中に密封した。この反応混合物を18時間にわたり180℃まで加熱した。冷却すると湿った赤色の固体が得られた。この生成物を100℃の真空下で3時間乾燥させ、ピンク色の固体生成物を得た。次にこの生成物を、例示的合成方法1に開示される方法に従って1000℃の流動するアンモニア中で熱分解した。
ZnO(2.2709g、28mmol)、Im(4.1942g、62mmol)、Fe(Ac)2(0.0655g、0.35mmol)、及び1,10−フェナントロリン(1.2330g、6.9mmol)を磨砕して均質な混合物にし、次にAr下でソルボサーマルボンベ中に密封した。この反応混合物を18時間にわたり180℃まで加熱し、ピンク色の固体生成物を得た。次にこの生成物を、例示的合成方法1に開示される方法に従って1000℃の流動するアンモニア中で熱分解した。
Claims (19)
- 酸素還元反応(ORR)触媒の製造のための方法であって、
0.7cm3g−1以上の内部細孔比容積を有する金属有機骨格(MOF)材料を提供することと、
鉄源及び/又はコバルト源を提供することと、
前記MOF材料を前記鉄源及び/又はコバルト源と一緒に熱分解して前記触媒を形成することと
を含み、
前記MOF材料が窒素を含み、且つ/又は前記MOF材料が窒素源並びに前記鉄源及び/又はコバルト源と一緒に熱分解される方法。 - 前記MOF材料が、Zn、Mg、Cu、Ag、及びNiから選択される遷移金属、又はそれらの2つ以上の組み合わせを含む、請求項1に記載の方法。
- 前記遷移金属が亜鉛を含む、請求項2に記載の方法。
- 前記MOF材料がゼオライトイミダゾレート骨格(ZIF)材料である、請求項1から3の何れか一項に記載の方法。
- 前記MOF材料が0.9cm3g−1以上の内部細孔比容積を有する、請求項1から4の何れか一項に記載の方法。
- 前記鉄源及び/又はコバルト源が、鉄及び/又はコバルトの塩である、請求項1から5の何れか一項に記載の方法。
- 前記MOF材料の熱分解が700−1500℃の温度で実施される、請求項1から6の何れか一項に記載の方法。
- 前記窒素源が、窒素含有配位子、好ましくは1,10−フェナントロリンを含む、請求項1から7の何れか一項に記載の方法。
- 熱分解が、アルゴン、窒素、アンモニア、若しくは水素、又はそれらの混合物を含む雰囲気下で実施される、請求項1から8の何れか一項に記載の方法。
- 熱分解が、不活性雰囲気下での第1の工程と、アンモニア、水素、二酸化炭素、及び/又は一酸化炭素を含む雰囲気下での第2の工程との2つの工程で実施される、請求項1から9の何れか一項に記載の方法。
- 前記MOF材料が、最長サイズが200nm以下の平均結晶サイズを有する、請求項1から10の何れか一項に記載の方法。
- 前記MOF材料が、導電性支持体上に提供される、請求項1から11の何れか一項に記載の方法。
- ORR触媒の製造のための方法であって、
最大空洞サイズが12Å以上の等方性空洞形状を有する金属有機骨格(MOF)材料を提供することと、
鉄源及び/又はコバルト源を提供することと、
前記MOF材料を前記鉄源及び/又はコバルト源と一緒に熱分解して前記触媒を形成することと
を含み、
前記MOF材料が窒素を含み、且つ/又は前記MOF材料が窒素源並びに前記鉄源及び/又はコバルト源と一緒に熱分解される方法。 - 酸素還元反応(ORR)触媒の製造のための方法であって、
金属有機骨格(MOF)配位子及びMOF金属源を提供することと、
鉄源及び/又はコバルト源を提供することと、
任意選択的に、窒素源を提供することと、
0.7cm3g−1以上の内部細孔比容積を有するMOF材料を含む触媒前駆体を提供するのに十分なエネルギー源を提供することと、
前記触媒前駆体を熱分解して前記ORR触媒を提供することと
を含む方法。 - 酸素還元反応(ORR)触媒の製造のための方法であって、
金属有機骨格(MOF)配位子及びMOF金属源を提供することと、
鉄源及び/又はコバルト源を提供することと、
任意選択的に、窒素源を提供することと、
最大空洞サイズが12Å以上の等方性空洞形状を有するMOF材料を含む触媒前駆体を提供するのに十分なエネルギー源を提供することと、
前記触媒前駆体を熱分解して前記ORR触媒を提供することと
を含む方法。 - 請求項1から15の何れか一項に記載の方法によって得られるORR触媒。
- 前記触媒及びポリマーを含むインク組成物を形成することを更に含む、請求項1から15の何れか一項に記載の方法。
- 請求項17に記載の方法によって得られるインク組成物。
- 請求項16に記載のORR触媒を含む燃料電池燃料電池のためのカソード電極。
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GBGB1515869.4A GB201515869D0 (en) | 2015-09-08 | 2015-09-08 | Oxygen reduction reactor catalyst |
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PCT/GB2016/052774 WO2017042564A1 (en) | 2015-09-08 | 2016-09-08 | Oxygen reduction reaction catalyst |
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GB201802781D0 (en) | 2018-04-04 |
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GB2557499B (en) | 2021-09-15 |
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